Process for the preparation of a coating, a coated substrate, an adhesive, a film or sheet

ABSTRACT

The invention comprises a process for the preparation of a coating, adhesive, film or sheet. In this process a mixture of a polyisocyanate functional, a polyepoxide functional, a polyanhydride functional or a polyketone functional compound or polymer and a compound containing reactive hydrogen, in which the compound containing reactive hydrogen is used in a material which is non-reactive towards the compound containing reactive hydrogen which mixture is not or low reactive at ambient conditions and high reactive under selected conditions, is applied onto a substrate at ambient temperature, followed by reacting the above compounds at elevated temperatures. At ambient temperature said compound containing reactive hydrogen is a solid material, a powder, a granule, a flake or grind or a mixture thereof which is preferably ground. The invention comprises further the coating mixtures to be used in the process and the coatings, coated substrates, adhesives, films, sheets, impregnated substrates, synthetic leathers, inmould coatings, coated leathers, coated polyvinylchlorides, coated non-wovens, coated coagulated polyurethane substrates, breathable coated substrates, obtained by applying the process.

The present invention relates to a process to prepare a coating,adhesive, film or sheet, of the thus obtained products and to thecoating mixture to be used in the process.

Several methods have been developed for high solids or solvent freeapplication in the polyurethane industry to prepare coatings or films.

One approach is the reaction of a polyisocyanate or of a isocyanatefunctional polyurethane prepolymer with a polyol at 160-180° C. In thisway flexible coatings can be prepared with a medium strength. Adisadvantage of this method is that the potlife of the mixture islimited to about 3 hours.

Further, while a reaction within 2 to 3 min is required, there is only apartial reaction within that time and a post reaction takes placebetween the unreacted components during storage at ambient temperature.As a consequence the coatings are sometimes tacky immediately after thecuring and for example a coated piece of textile cannot be rolled up.

A second approach is the reaction between a blocked polyisocyanate and apolyamine or polyol. Especially with polyamines strong films can beobtained. When the blocking agent is a ketoxime, such as butanone oxime,it will evaporate during the reaction, but usually some of the butanoneoxime will stay in the film. The result is that, also after application,their may be toxic vapours and the coating smells. Other types ofblocking agents, such as dimethylpyrazole and triazole types, malonicesters or acetoacetates, and ε-caprolactams need a long deblocking timeand they will partially stay in the coating as not-polymerizedmolecules. Also in these cases the coatings smell.

A further possibility is the combination of a polyisocyanate and apolyamine from which the amine functions are deactivated by the reactionwith a maleic ester under formation of a aspartate. In spite of thedeactivation of the amine functions the combination with apolyisocyanate will have a too limited potlife.

An alternative method is the use of internally blocked polyisocyanateswhich act as crosslinkers mainly in powder coatings. In this method anincorporated uretdion acts as internal blocking agent. At prolongedheating the uretdion unblocks under formation of two isocyanatefunctions, which further react with a material containing reactivehydrogen. The curing time at 180° C. is at least 15 min, which is anunacceptable long time for our applications.

All these systems have some negative aspects such as a to short potlife,a to long reaction time and the evaporation of toxic vapours. We haveovercome the described problems and have now developed a new process toprepare a coating, adhesive, film or sheet by a heat curable system.

DESCRIPTION OF THE INVENTION

According to the present invention there is provided a process for thepreparation of a coating, adhesive, film or sheet, characterized in thata mixture of a polyisocyanate functional, a polyepoxide functional, apolyanhydride functional or a polyketone functional compound or polymerand a compound containing reactive hydrogen, in which the compoundcontaining reactive hydrogen is dispersed in a material which isnon-reactive towards the compound containing reactive hydrogen, whichmixture is not or low reactive at ambient conditions and high reactiveunder selected conditions, is applied onto a substrate at ambienttemperature, followed by reacting the above compounds at elevatedtemperatures.

Surprisingly, the technical problems known in the art are solved andcoatings, adhesives, films or sheet are obtained in an easy way by theproces of the invention. Surprisingly, it further appeared that thepotlife of the coating mixtures of the invention is relatively long, thereaction is relatively fast and no toxic vapours are evaporated from theobtained products.

Since the material containing reactive hydrogen is not or low reactiveat ambient temperature towards a polyisocyanate functional, apolyepoxide functional, a polyanhydride functional, or a poly ketonefunctional compound or polymer such mixtures will have a long pot-life,which is a great advantage in the process. This means, at ambienttemperature, such a mixture will be stable for at least 1 day. Severalof the compounds containing reactive hydrogen are that inert in apolyketone, polyepoxide or polyanhydride functional compound or polymerthat the mixtures are stable as a one pot system.

The material containing reactive hydrogen, is not or low-reactive atambient temperature because under these conditions the mixture of theisocyanate functional material and the material containing reactivehydrogen form a two phase system, which means it is a heterogeneoussytem. In the two phase sytem the compound containing reactive hydrogenis present in the mixture as a solid, a powder, a granule, a flake or agrind or a mixture thereof. The material is preferably ground to obtaina greater reactive area.

The compound containing reactive hydrogen is preferably dispersed in asecond material, which material is non-reactive towards said compoundcontaining reactive hydrogen, and not or low reactive towards theisocyanate functional-, the epoxide functional-, the anhydridefunctional- or the ketone functional compound or polymer at ambienttemperature before the desired reaction is effected.

Such a dispersion is obtained by dispersing the material containingreactive hydrogen, in the second material by conventional methods whichmay be by a for example a disperser or a pearl mill. By dispersing thecompound containing reactive hydrogen in an inert material a smallerparticle size and a greater area can be obtained than when the puresolid is ground.

The compound containing reactive hydrogen reacts fast with apolyisocyanate functional, a polyepoxide functional, a polyanhydride, ora polyketone functional compound or polymer under selected conditions.Such a condition may be a sudden increase of temperature. At that momentthe material containing reactive hydrogen will melt or dissolve in thesystem, the reactive sites of the molecules can move freely, and whilethe mixture is homogenised by diffusion, the reaction with thepolyisocyanate functional, the polyepoxide functional, the polyanhydridefunctional, or the polyketone functional compound or polymer occurs.

The homogenisation at higher temperatures will be more efficient and asa result the reaction will be faster and more complete. Moreover, theperformance of the films or coatings will be better when the particlesize of the material containing reactive hydrogen, is small.

An excellent film or coating quality is obtained when the particle sizeis between 0,5 and 200 μm. A more preferable particle size is between0,5 and 60 μm and the most preferable size is between 0,5 and 15 μm.

To obtain a maximal potlife, the material containing reactive hydrogenmay not melt or soften in the reaction mixture at ambient temperature.

Several types of material containing reactive hydrogen may be used inthe process such as polyhydrazides, polysemicarbazides, polysulphonylhydrazides, carbohydrazide, guanidine or guanidine salts, polyamines orpolyamine salts.

Said polyhydrazide which may be used in the process of the invention maybe oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, adipicdihydrazide, sebacic dihydrazide, dodecanoic dihydrazide, isophthalicdihydrazide, piperazine N,N′-dihydrazide, m-benzene-dihydrazide,p-benzene-dihydrazide.

Preferably adipic dihydrazide and carbodihydrazide are used since theyare inert in the reaction mixtures with an epoxide functional-, ananhydride functional- or a ketone functional compound or polymer atambient temperature for at least one year. They further reactsinstantaneously with a polyisocyanate, a polyepoxide, a polyanhydride ora polyketone functional compound or polymer at temperatures of 80-180°C. or higher.

A polysemicarbazide which may be used in the process of the invention isselected from ethane-disemicarbazide, butane-disemicarbazide,propane-disemicarbazide, hexane-disemicarbazide,para-benzene-disemicarbazide, toluene-2,4-disemicarbazide,toluene-2,4-disemicarbazide, bis (4-semicarbazido-phenyl)ether, bis(4,4′-hydrazido)-3,3′-dimethoxy biphenyl, di-N,N′-methylamino urea,4,4′-methylene-bis (cyclohexene semicarbazide),3-semicarbazidomethyl-3,5,5-trimethylcyclohexyl-semicarbazide ormixtures thereof.

A polysulphonylhydrazide which may be used in the process of theinvention is selected from p,p′-oxybis benzene sulphonyl hydrazide;bis(methylhydrazido)sulphate, bis (methylhydrazidosulphonyl)piperazine,or bis p-(hydrazidosulphonylamino)benzene.

Usually, guanidine hydrochloride, guanidine acetate, guanidine carbonateand guanidine nitrate are suitable a guanidine salts.

A suitable polyamine or polyamine salt may be piperazine, piperazinediacetate, piperazine dihydrochloride, lysine, lysine hydrate,diaminoisophorone diacetate, diaminoisophorone dihydrochloride.

As mentioned before it is preferable when the compound containingreactive hydrogen is used as a dispersion in a material which is inertto both the reactive hydrogen compound and the second reagent of thereaction. This material is preferably a polyether, a polyester, apolycarbonate, a polyacrylate, a polyvinylalkylether, a polyurethane,optionally substituted by substituents which are non reactive towardsthe material containing reactive hydrogen, and non- or low reactivetowards the isocyanate functional material or is a plasticizer of thegroup of phthalic alkylesters, adipic alkyl esters, sebacic alkylesters, dodecanoic alkyl esters, polyesters, phosphate esters, fattyesters, straight and modified natural or mineral oils, sulphonated oils,ethoxylated oils, epoxidised oils, fatty acids, sulphon amides, fatliquors, lecithine or a mixture thereof, optionally mixed with water.

An important aspect of the invention is that a low solvent level can beused during the process, and most preferably the process is solventfree.

In the process of the invention a polyisocyanate functional compound orpolymer, a polyketone functional compound or polymer, a polyepoxidefunctional compound or polymer, or a polyanhydride functional compoundor polymer and the material containing reactive hydrogen are mixedtogether in an stoichiometric ratio of 0.5 to 1.5, and preferably in aratio of 0.9 to 1,2, whereafter the obtained mixture is applied onto asubstrate and the covered or impregnated substrate is heated to atemperature of 50 to 300° C. for 1-20 min and preferably to 80 to 200°C. for 1 to 10 min.

Surprisingly it appeared that the reaction takes place as well when thepolyisocyanate functional compound or polymer and the materialcontaining reactive hydrogen are mixed together in a stoichiometricratio of 0.5-1.5 and preferably in a ratio of 0.9-1.1 whereafter theobtained mixture is applied onto a substrate and the covered orimpregnated substrate is immersed into water of 20 to 100° C. for 0.5 to10 min.

The isocyanate functional compound or polymer which is used in theprocess of the invention is usually a polyisocyanate or aisocyanate-functional polyurethane prepolymer.

Urea functions are formed by the reaction of the isocyanate functionsand the NH₂-functions of the material containing reactive hydrogen.

The ketone functional compound or polymer of the invention is preferablya ketone functional polymer polyurethane with in-chain, pendant and/orterminal ketone functions. Ketimine functions are formed by the reactionof the ketone and the NH₂-functions of the material containing reactivehydrogen.

The anhydride functional compound of the invention is usually apolyanhydride or a copolymer containing anhydride functions. Amidefunctions are formed by the reaction of the anhydride function and theNH₂-functions of the the material containing reactive hydrogen.

The epoxide functional compound of the invention is usually apolyepoxide or a epoxy functional polymer. The epoxide rings are openedduring the reaction with the NH₂-functions of the material containingreactive hydrogen and secundairy ore tertiary amines are formed.

A further part of the invention are the coatings, coated substrates,adhesives, films, sheets, impregnated substrates, synthetic leathers,inmould coatings, coated leathers, coated polyvinylchlorides, coatednon-wovens, coated coagulated polyurethane substrates, breathable coatedsubstrates which are obtained by the process of the invention.

The thus obtained films or coatings are strong, dry, flexible andUV-resistant.

The process and application results of the present invention areprofitable regarding to conventional heat curable systems which arelow-solvent or solvent-free. Regarding to the system in which apolyisocyanate functional compound or polymer reacts with a polyol themixture of the present invention has a longer pot life, while thereaction is faster, almost instantaneous, and more complete at elevatedtemperatures. The obtained films or coatings are stronger because in theprocess of the invention urea functions are formed by the reaction ofthe isocyanate function and the amine or hydrazide, while in thereaction of a isocyanate and a OH-function a urethane function isformed. It is wellknown that an urea function gives additional strengthbecause of the presence of hydrogen at the N of the urea function whichmakes it possible to form hydrogen bridges.

Regarding to the systems in which blocked isocyanates are used incombination with polyamines films or coatings of comparable strength areformed by the process of the invention, but the elongation and thetension at break is larger. The potlife of the mixture of the presentinvention is longer, there are no evaporating toxic reactants such asbutanone oxime, or remaining low molecular material such asdimethylpyrazole and triazole types, malonic esters or acetoacetates andthe resulting films or coatings do not smell. As a consequence theprocess of the invention will not have any damaging effect on theenvironment.

Regarding to the systems in which a polyisocyanate is reacted with apolyamine from which the amine functions are deactivated by the reactionwith a maleic ester under formation of a aspartate, the mixtures of theprocess of the invention have a much longer potlife.

Regarding to the system in which an incorporated uretdion acts asinternal blocking agent the reaction time is much shorter at elevatedtemperatures.

Finally the invention provides a coating mixture comprising on the oneside a isocyanatefunctional compound, a polyepoxide functional compound,a polyanhydride functional compound, or a polyketone functional compoundand on the other side a compound containing a reactive hydrogen which isnot or low reactive at ambient temperature and highly reactive underselected conditions, which coating mixture is applied in the process ofthe present invention.

The coating mixture of the invention is stable at ambient temperaturefor at least one day and preferably the coating mixture of the epoxidefunctional-, the anhydride functional- or the ketone functional compoundor polymer and the compound containing reactive hydrogen is stable atambient temperature as a one pot system.

The compound containing reactive hydrogen is present in the mixture as asolid, a powder, a granule, a flake or a grind or a mixture thereof andis preferably ground.

As mentioned before it is preferable when the compound containingreactive hydrogen is used as a dispersion in a material which is inertto both the reactive hydrogen compound and the second reagent of thereaction.

The particle size of the ground or of the dispersion of the compoundcontaining reactive hydrogen is from 0,5 to 200 μm, preferably from 0.5to 60 μm and most preferably from 0.5 to 15 μm.

The mixtures of the isocyanate functional material and the materialcontaining reactive hydrogen, may be applied onto a substrate. They maybe used as films, sheets, in adhesives, sealants, printing ink and incoatings. They may be applied on any substrates, including leather orartificial leather, metals, wood, glass, plastics, paper, paper board,textile, non-woven, cloth, foam and the like by conventional methods,including spraying, flow-coating, reverse-coating, brushing, dipping,spreading and the like. The cured material may be further treated withcoatings, such as a top-coat, or adhered to any sustrate by direct ortransfer coating technics.

Many additives may be present for application reasons, for examplefillers, colorants, pigments, silicons, fire retardants, matting agents,flow agents, foaming agents and the like.

Some applications where the process of the invention is used are ofspecial interest.

For example, the process may be used for the preparation of a coatedtextile to be used as a synthetic leather. Such a process may comprisethe preparation of an adhesion coat onto textile, followed by applying amixture of a polyurethane prepolymer and a hydrazide-, semicarbazide-,amine or amine salt-dispersion of the invention onto the adhesion coatand curing of this mixture at an elevated temperature, which may bebetween 80 and 250° C. The coating may further be embossed at 80 to 250°C.

By repeating of the process described above on the backside of thetextile a double sided coated textile may be obtained.

Alternatively the process may be used for the preparation of a coatedsubstrate to be used as synthetic leather by transfer coating, which maycomprise the preparation of a skincoat onto release paper, followed bythe preparation of an intermediate coat by applying a mixture of apolyurethane prepolymer and a hydrazide-, semicarbazide-, amine or aminesalt-dispersion of the invention onto the skincoat and curing of thismixture at an elevated temperature, which may be between 80 and 250° C.,whereafter an adhesive coat is applyed onto the intermediate coat inwhich a piece of textile is laminated and the thus obtained material isdried, whereafter the release paper is removed.

The process described above may also be used for the preparation of forexample coated leather, coated polyvinyl chloride, coated non-woven,coated coagulated polyurethane substrates.

Alternatively the process may be used for the preparation of a coatedpolyvinyl chloride to be used as synthetic leather by transfer coating,which may comprise the preparation of a skincoat onto release paper,followed by the preparation of an intermediate coat by applying amixture of a polyurethane prepolymer and a hydrazide-, semicarbazide-,amine or amine salt-dispersion of the invention onto the skincoat andcuring of this mixture at an elevated temperature, which may be between80 and 250° C., whereafter a compact polyvinylchloride substrate ontothe high solids coat is prepared by applying a polyvinylchloride pasteonto the high-solids coat, optionally followed by laminating of a pieceof textile into the polyvinylchloride paste, and curing of the polyvinylchloride paste.

The process may further be used in the preparation of a moulded materialby inmould coating which comprises spraying of a mixture of apolyurethane prepolymer and a hydrazide-, semicarbazide-, amine or aminesalt-dispersion of the invention, and optionally a non-reactive solventinto a matrix until a desired coating thickness is obtained. The matrixmay be heated during the spray process, or after the spraying process.After the curing the moulded material may be removed.

Various aspects of the present invention are illustrated by thefollowing examples. These examples are only illustrative of theinvention and are not limiting the invention as claimed hereafter.

EXAMPLES Example 1

Preparation of an aliphatic polyether based isocyanate functionalpolyurethane prepolymer.

Under a nitrogen atmosphere 112.78 g (507.56 mmole) of3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (hereafterrefered to as IPDI) was added to a mixture of 139.21 g (138.24 mmole) ofa polypropylene glycol with a molecular weight of 1007, 163.77 g (81.89mmole) of a propylene glycol with a molecular weight of 2000 and 4.2 g(31.34 mmole) of trimethylol propane at 60-70° C. while stirring. Themixture was heated to 100° C. and reacted at this temperature for 2 hrsto form a polyurethane prepolymer. After 1 hr of reaction time 0.1 g oftinoctoate was added as a catalyst. The reaction mixture was cooleddown. The amount of remaining NCO was measured and appeared to be 4.43%.

Example 2

Preparation of an aliphatic polyester based isocyanate functionalpolyurethane prepolymer.

Under a nitrogen atmosphere a 107.12 g (482 mmole) of IPDI was added toa mixture of 141.81 g (151.67 mmole) of a polyester diol with amolecular weight of 935 available from Occidental as Ruco S 1015-120,166.83 g (55.61 mmole) of a polyesterdiol with a molecular weight of3000 available from Occidental as Ruco S 1015-35 and 4.2 g (31.34 mmole)of trimethylol propane at 60-70° C. while stirring. The mixture washeated to 100° C. and reacted at this temperature for 2 hrs to form apolyurethane prepolymer. After 1 hr of reaction time 0.1 g of tinoctoatewas added as a catalyst. The reaction mixture was cooled down. Theamount of remaining NCO was measured and appeared to be 3.99%.

Example 3

Preparation of an aromatic polyether based isocyanate functionalpolyurethane prepolymer.

The procedure of example 1 was repeated with the exception that the IPDIwas replaced by 88.31 g (507.56 mmole) of toluene diisocyanate(hereafter referred to as TDI) and the reaction was executed at 90-95°C. The NCO amount appeared to be 4.60.

Example 4

Preparation of an aromatic polyester based isocyanate functionalpolyurethane prepolymer.

The procedure of example 2 was repeated with the exception that the IPDIwas replaced by 85.61 g (492 mmole) of TDI and the reaction was executedat 90-95° C. The NCO amount appeared to be 4.23%.

Example 5

Preparation of a ketone functional polyurethane polymer from aisocyanate functional polyurethane prepolymer and hydroxyacetone.

Under a nitrogen atmosphere a mixture of 100 g of the polyurethaneprepolymer from example 1 and 7.81 g (105.48 mmole) of hydroxyacetonewere heated to 100° C. The mixture was stirred for 2 hrs at 100° C.After 1 hr of reaction time 0.1 g of tinoctoate was added as a catalyst.

The disappearance of NCO was checked by IR-spectroscopy by following theNCO signal at 2269 cm⁻¹.

Example 6

Preparation of a ketone functional polyurethane polymer.

Under a nitrogen atmosphere 68.42 g (308 mmole) of IPDI was added to 251g (171 mmole) of a ketone functional polyester diol obtainable fromNeoResins as PEC 205 in 80 g of dipropylene glycole dimethyl ether at60° C. while stirring. The mixture was heated to 100° C. and reacted atthis temperature for 2 hrs to form a polyurethane prepolymer. After 1 hrof reaction time 0.1 g of tinoctoate was added as a catalyst. Thereaction mixture was cooled down. The amount of remaining NCO wasmeasured using a sample of 10 g, and appeared to be 2.71.

18.65 g (252 mmole)of methoxyethylamine was added to the obtainedpolyurethane prepolymer and the mixture was stirred for is min at 20° C.The disappearance of NCO was checked by IR-spectroscopy by following theNCO signal at 2269 cm⁻¹.

Example 7

Preparation of a ketone functional polyurethane polymer from aisocyanate functional isocyanurate and hydroxyacetone.

Under a nitrogen atmosphere a mixture of 151 g (259 mmole)N,N′,N″-triisocyanatohexylisocyanurate and 57.50 g (777 mmole) ofhydroxyacetone in 52.13 g of dipropylene glycol dimethyl ether wereheated to 90° C. The mixture was stirred for 2 hrs at 90° C. After 1 hrof reaction time 0.1 g of tinoctoate was added as a catalyst. Thedisappearance of NCO was checked by IR-spectroscopy by following the NCOsignal at 2269 cm⁻¹.

Example 8

Comparative example: preparation of a film from a MEK-oxime blockedpolyurethane polymer and a amine functional crosslinker.

9.39 g (105.48 mmole) of mekoxime was added to 100 g of the prepolymerof example 1 at 60-65° C. The mixture was stirred for 2 hrs at 70° C.The disappearance of the NCO was checked by the absence of theNCO-signal in the Infrared spectrum at 2270 cm⁻¹. The product was cooleddown and mixed with 12.47 g (52.4 mmole) of3,3′-dimethyl-4,4′-diamino-dicyclohexyl-methan and 0.1 g of a 10%solution of dibutyltinlaureate in dipropylene glycol dimethyl ether ascatalyst.

200 μm films were prepared and cured at 180° C. for 5 min.

Example 9

Comparative example: preparation of a film from a OH-functionalpolyurethane polymer and a NCO-crosslinker.

A: preparation of the OR-functional polyurethane polymer:

Under a nitrogen atmosphere 264 g (132 mmole) of a polypropyleneglycolwith a molecular weight of 2000 and 7.92 (88 mmole) of 1,3-butanediolwere heated to 80° C. 97.68 (440 mmole) of IPDI was added and themixture was, stirred for 2 hrs at 100° C. After 1 hr of reaction time0.1 g of tinoctoate was added as a catalyst. The reaction mixture wascooled down and the amount of remaining NCO in the resulting prepolymerwas determined by titration and appeared to be 4.6%. 36.21 g (402 mmole)of 1,3-butanediol and 0.1 g of dibutyl tinlaureate were added and themixture was heated to 100° for two hrs. The disappearance of the NCO waschecked by the absence of the NCO-signal in the Infrared spectrum at2270 cm⁻¹. The product was cooled down and had an OR-amount of 2.13meq/g.

B: preparation of an NCO-crosslinker: 14.4 g (240 mmole) of n-propanolwas added within 30 min to 102.2 gr (containing 600 mmole of NCO) ofN,N′,N″-triisocyanatohexylisocyanurate, whereafter the mixture wasstirred and heated at 800 for 2 hrs. After 1 hr of reaction time 0.1 gof tinoctoate was added as a catalyst. The reaction mixture was cooleddown and the amount of remaining NCO in the resulting polymer wasdetermined by titration and appeared to be 12.0.

A 200 μm film was prepared from a mixture of 13 gr of the product of Aand 9.2 g of the product of B with 0.05 g of a 10% solution ofdibutyltinlaureate in dipropylene glycol dimethyl ether as catalyst. Thefilm was cured for 5 min at 160° C.

Example 10

Preparation of a semicarbazide from4,4′-methylene-bis(cyclohexylisocyanate) and hydrazine.

26.2 g (100 mmole) of 4,4′-ethylenebis(cyclohexylisocyanate) in 26.2 gof dipropylene glycol dimethyl ether was added to 12 g (240 mmole) ofhydrazine hydrate in 18 g of isopropanol and 12 g of of dipropyleneglycol dimethyl ether while keeping the temperature below 25° C. bycooling with ice. A white precipitate appeared. After stirring for 30min the precipitate was filtered of and rinsed with dipropylene glycoldimethyl ether. The product was dried at 80° C. The yield was 44.42g=88.9% from the theoretical amount.

Example 11

Preparation of a semicarbazide from hexamethylene diisocyanate andhydrazine.

33.6 g (200 mmole) of hexamethylenediisocyanate in 33.6 g of dipropyleneglycol dimethyl ether was added to 24 g (480 mmole) of hydrazinehydratein 27 g of isopropanol and 24 g of of dipropylene glycol dimethyl etherwhile keeping the temperature below 25° C. by cooling with ice. A whiteprecipitate appeared. After stirring for 30 min the precipitate wasfiltered of and rinsed with dipropylene glycol dimethyl ether. Theproduct was dried at 80° C. The yield was 41.95 g=84.9% from thetheoretical amount.

Example 12

Preparation of a semicarbazide from a commercial mixture of toluenediisocynate and hydrazine.

34.8 g (200 mmole) of a commercial mixture of toluene diisocynate in33.6 g of dipropylene glycol dimethyl ether was added to 24 g (480mmole) of hydrazine hydrate in 24 g of isopropanol and 24 g of waterwhile keeping the temperature below 25° C. by cooling with ice. A whiteprecipitate appeared. After stirring for 30 min the precipitate wasfiltered of and rinsed with dipropylene glycol dimethyl ether. Theproduct was dried at 80° C.

The yield was 34.78 g=69.3% from the theoretical amount.

Example 13

Preparation of a semicarbazide from3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate and hydrazine.

44.4 g (200 mmole) of IPDI in 33.6 g of dipropylene glycol dimethylether was added to 24 g (480 mmole) of hydrazine hydrate in 24 g ofisopropanol and 24 g of water while keeping the temperature below 25° C.by cooling with ice. The mixture was stirred for 1 hr and the solventswere evaporated. The mixture was cristalized from isopropanol.

Example 14

Preparation of a grind and of a dispersion of adipic dihydrazide.

Adipic dihydrazide was ground as a pure powder or it was ground in a 1:1weight ratio in di(ethylhexyl) adipate in the presence of 0.5% of TritonX-100. By increasing the dispersioning time and the speed of thestirring blade smaller particle sizes could be obtained. The grinds anddispersions which were obtained are presented in Table I. The range ofthe particle size in the dispersions were measured by microscopy.

TABLE 1 Particle sizes of adipic dihydrazide in a pure grind or as adispersion in di(ethylhexyl) adipate particle size of adipic dihydrazidein the medium (μm) Example medium Range 14 A Pure  30-300 14 B pure,ground  30-250 14 C di(ethylhexyl)adipate  40-150 14 Ddi(ethylhexyl)adipate 30-60 14 E di(ethylhexyl)adipate  5-40 14 Fdi(ethylhexyl)adipate 0.5-13 

Example 15

Preparation of a dispersion of adipic hydrazide in different liquidmaterials which are none non-reactive towards the adipic dihydrazide.

Adipic hydrazide was dispersed in a 1:1 weight ratio in liquid materialswhich were non-reactive towards the adipic dihydrazide in the presenceof 0.5% of Triton X-100 by a Dispermat pearl mill configuration for 1.5hrs at 5000 rpm. The range of the particle size in the dispersionsdepending on the medium were measured by microscopy. The results arepresented in Table 2. The results show that the values for the particlesize in a more polar medium are slighly less than in an apolar medium.

TABLE 2 Particle size of adipic dihydrazide as dispersion in severalmedia particle size of adipic dihydrazide in the medium (μm) Examplemedium range 15A di(ethylhexyl)adipate 30-60 15B dibutyl phtalate 30-6015C dioctyl phtalate 30-60 15D dibutyl sebacate 30-60 15E polyethyleneglycol 10-30 15F tributoxyethylphosphate 10-30 15G soybean lecithin10-30 15H castor oil 10-30 15I N-methyl pyrrolidone 10-30 15Jdipropylene glycol 10-30 dimethylether

Example 16

Preparation of a dispersion of several dihydrazides, disemicarbazides, adi(sulphonylhydrazide), amine salts.

Several dihydrazides, disemicarbazides, sulphonyldihydrazides anddiamine salts were ground in di(ethylhexyl) adipate or in tributoxyethylphosphate or in N-methylpyrroli-don by a Dispermat pearl millconfiguration for 1.5 hrs at 5000 rpm. The products which were groundwere: carbodihydrazide, oxalic dihydrazide, succinic dihydrazide, adipicdihydrazide, sebacic dihydrazide, dodecanoic dihydrazide, isophtalicdihydrazide, the products of example 10, 11, 12 and 13,4,4′-oxybis(benzenesulphonylhydrazide), guanidine hydrochloride, lysine.

In all cases the particle sizes of the hydrogen reactive materials inthe dispersions were measured by microscopy. The ranges indi(ethylhexyl) adipate were comparable and were between 30 and 60 μm.The values in tributoxyethyl phosphate or in N-methylpyrrolidon wereslightly less and were 10-30 μm.

Example 17

Kinetics of the curing of the prepolymers of example 1, 2, 3 and 4 withadipic dihydrazide at several temperatures and times, measured byinfrared spectroscopy.

The reaction of the prepolymers of example 1, 2, 3 and 4 with the adipichydrazide dispersion of example 15 A (containing 5.716 meq ofhydrazide/g) was followed at several temperatures by infraredspectroscopy. Further the potlife of the mixtures at 50° C. werecontroled.

50 gr of a polyurethane prepolymer of example 1, 2, 3, or 4 was mixedwith a stoichiometric amount of the adipic dihydrazide dispersion and afilm was prepared onto a sodium chloride cell. An Infrared spectrum wasprepared which showed a large NCO signal at 2260 cm⁻¹. The cell washeated at 140, 160 or at 180° C. for several minutes and the decrease ofthe NCO-signal was measured by IR-spectroscopy. The results arepresented in Table 3.

The results show that the IPDI-based prepolymers from example 1 and 2are more reactive than the TDI-based prepolymers from example 3 and 4,which is indicated by a faster disappearance of the NCO-signal. There isnot a significant difference in reactivity between the polyether and thepolyester prepolymers.

Further the mixtures were stable for at least 6 weeks at 50° C. and atthat moment the intensity of the signals of the NCO in the IR-spectrumwere comparable with that of the freshly prepared mixtures.

TABLE 3 decrease of the NCO signal in the infrared spec- trum during thecuring reaction of isocyanate functional prepolymers of example 1, 2, 3and 4 with an adipic acid dispersion in di(ethylhexyl) adipate ProductCuring of Temperature amount of remaining NCO (%) after^(a) Example (°C.) 4 min 6 min 9 min 15 min 1 140 19.0 5.7 2.5 1.2 160 1.5 0.3 0 0.3 2140 26.5 5.9 2.2 1.2 160 1.2 0.1 0 0 3 140 na 78.9 55.9 49.6 160 na 25.210.3 8.2 180 17.4 9 5.5 2.2 200 3.2 1.5 1.0 0.7 4 140 na 89.0 58.8 51.1160 na 49.7 11.5 8.5 180 19.4 9.8 5.6 2.4 200 5.4 2.7 1.5 1.2 Notes totable 3: ^(a)determined by measuring the area of the signal at 2260-70cm⁻¹ from the NCO-signal regarding to the carbonyl signal at 1740 cm⁻¹.^(b)na = not available

Example 18

Kinetics of the film formation by curing of the polurethane prepolymerof example 2 and 4 with adipic dihydrazide or carbodihydrazide atseveral temperatures and times.

50-gr of polyurethane prepolymer of example 2 (based on IPDI, which isan alifatic diisocyanate) or 4 (based on TDI, which is an aromaticdiisocyanate) were mixed with an stoichiometric amount of the adipicdihydrazide dispersion of example 15 A or of the carbodihydrazidedispersion of example 16 and the mixtures were applied onto releasepaper. The curing of the films was checked at 120, 140 and at 160° C. at1, 2, 3, 6 and 12 min. The results are presented in tabel 4. Both,aromatic and aliphatic prepolymers are completely reacted with thecarbodihydrazide or with the adipic dihydrazide after 3 min. at 160° C.Regarding to example 17 the reaction is faster because the sodiumchloride cell needs more time for warming up than release paper. Whenthe film formation was complete flexible films were obtained.

TABLE 4 Film formation by curing of a polyurethane prepolymer of example2 and 4 with adipic dihydrazide or carbo- dihydrazide at severaltemperatures and times poly- phase of the film^(a) urethane hydrogencuring at a curing time of of reactive temp. 1 2 3 6 12 example material(° C.) min min min min min 2 adipic 120 w w w t r dihydrazide 140 t r-ir r r 160 r-i r r r r 2 carbodi- 120 w w t t r hydrazide 140 t t r-i r r160 r-i r r r r 4 adipic 140 w w w w t dihydrazide 160 r-i r r r r 4carbodi- 140 r-i r r r r hydrazide 160 r-i r r r r Notes to Table 4^(a)w: the mixture is still wet; no reaction is observed t: the mixtureis tacky; a partial reaction is effected r-i: film formation iseffected, but the film is not strong, which means that the reaction isincomplete r: complete film formation is effected

Example 19

Preparation of films by curing a prepolymer of example 2 and adipichydrazide powder or dispersion of example 14 and measurement of thehomogenity of the films depending on the particle size of the adipicdihydrazide.

3.48 g (20 mmole) of ground adipic dihydrazide or 7.00 g (20 mmole) ofan adipic dihydrazide dispersion in di(ethylhexyl)adipate of example 15A was stirred into 50 g (containing 40 meq of NCO) of the prepolymer ofexample 2. Films of 200 μm were prepared onto a black coated glossypaper and heated for 3 min at 160° C. The gloss of the films wasmeasured by a reflectometer. Further films of 200μ were prepared ontransparant polyester sheets and the transparency of the films wasdetermined by measuring the transmision by spectroscopy at 550 nm on aHitachi model 101 spectrophoto-meter. The gloss and the transparancy ofthe films is a measure for the homogenity of the films The results ofthe tests are in table 5. It appeared that when the particle size of theadipic dihydrazide was small, the gloss and the transparency of thefilms were maximal.

TABLE 5 Homogeneity of cured films depending on the particle size of theadipic dihydrazide particle size of the adipic transmission Adipichydrazide dihydrazide of cured grind originated in the grind (μm) glossof cured films of from example range films of 200 μm 200 μm (%) 14 A 30-300 7.8 52.2 14 B  30-250 8.5 64.5 14 C  40-150 27 85.0 14 D 30-6046 93.5 14 E  5-40 60 94.6 14 F 0.5-13  95 97.0

Example 20

Preparation of a film by curing a polyether polyurethane prepolymer anda adipic dihydrazide dispersion and comparing the film with the film ofexample 8 and of example 9.

9.28 g (26.5 mmole) of an adipic dihydrazide dispersion of example 15 Awas stirred into 50 g (containing 53 meq of NCO) of the prepolymer ofexample 1. Films of 200 μm were prepared and reacted for 3 min at 160°C. The mechanical properties of the films were determined and comparedto those of the films of the high solid systems of comparative examples8 and 9. The results are shown in table 6.

The results show that regarding to the films of example 8 and 9 themaximal strength and elongation of the film of example 20 is muchhigher. The tensile strength at 100 and 200 MPa is much more than thatof example 9 and comparable with that of example 8. Regarding to example8 there is a further advantage that no butanone oxime is released.

TABLE 6 mechanical properties of the films of a polyether polyurethanecured with adipic di-hydrazide regarding to the films of example 8 andof example 9. Film of Mechanical properties (MPa)^(a) example M-100M-200 M-300 M400 UTS Elongation 8 2.6 3.8 — — 4.7 260 9 0.6 1.2 — — 1.3220 20 2.8 4.4 5.8 7.7 7.6 405 notes to table 6: ^(a)MPa is megapascal(10⁶ Nm⁻²). The mechanical properties and the elongation are measuredwith films which were stretched at a thickness of 200 μm on a MTSSynergie 200 apparatus. The values at M-100, M-200, M-300 and M400 givetensile strengths of the films while stretching them for respectively100, 200, 300 and 400%. The UTS is the ultimate tensile strength justbefore the film breaks. The elongation is the maximal elongation beforethe film breaks.

Example 21

Preparation of coatings on glass by curing a polyisocyanate and theadipic hydrazide dispersion of example 15A.

50 g of N,N′,N″-tris(6-isocyanatohexyl)isocyanurate or of,N,N′-bis(6-isocyanato-hexyl-N-(6-isocyanato-hexylamido)urea was mixedwith a stoichiometric amount of the adipic hydrazide dispersion ofexample 15A or of the carbodihydrazide dispersion of example 16. 200 μmfilms were prepared on glass and heated for 6 min is at 160° C. Hardcoating surfaces were obtained with a good adhesion to the glass.

Example 22

Preparation of a film by curing a polyurethane prepolymer and adispersion of a hydrogen reactive material of example 16.

50 g of the polyurethane prepolymer of example 2 was mixed with astoichiometric amount of the dispersions of example 16 and the mixtureswere applied onto release paper. The curing of the films was checked at140 or 160° C. after 3 min and after 12 min. When no film formation wasobserved the curing was checked at 220 and 250° C. The results arepresented in tabel 7.

The results show that the dihydrazides, disemicarbazides and somediamine salts react with a isocyanate functional polyurethane prepolymerto form a film. These films are flexible. The table further shows thatthe reactivity of the used dihydrazides is comparable with that of thesulphonyldihydrazide used and both are are more reactive than thesemicarbazides used. The amine salts need a prolonged heating at highertemperatures before they react.

TABLE 7 Film formation by curing the polyurethane prepolymer of example2 and a dihydrazide, disemicarbazide, and a diamine phase of thefilm^(a) at a curing temperature and time of 140° C. 160° C. 220° C.250° C. Hydrogen 3 12 3 12 3 12 3 reactive material min min min min minmin min carbodihydrazide r-i r r r — — — oxalic dihydrazide t r r r — —— succinic dihydrazide t r r r — — — adipic dihydrazide r r r r — — —sebacic dihydrazide r r r r — — — dodecanoic r r r r — — — dihydrazideisophtaltic r r r r — — — dihydrazide 4,4,- w w w t r — — methylenebis-(cyclohexylisemi- carbazide) hexamethylene w w t r r — — disemicarbazidetolyldiaemicarbazide w w w t r — — 3-semicarbazido- w w w r-i r — —methyl-3,5,5- trimethylcyclo- hexylsemi- carbazide 4,4′- r r r r — — —oxybis- (benzenesulphonyl- hydrazide) guanidine- w w w w w r r-ihydrochloride lysine w w w w t r r-i Notes to Table 7 ^(a)w: the mixtureis still wet; no reaction is observed t: the mixture is tacky; a partialreaction is effected r-i: film formation is effected, but the film isnot strong, which means that the reaction is incomplete r: complete filmformation is effected

Example 23

Preparation of a film by curing a polyepoxide and a adipic dihydrazideor a carbodihydrazide dispersion 50 g (138.7 mmole) of Tetrad-X, whichis a polyepoxide material obtainable from Mitsubishi, was mixed with astoichiometric amount of the adipic hydrazide dispersion of example 15 Aor the carbodihydrazide of example 16. The products were applied ontorelease paper and heated at 140 and at 160° C. The mixtures were curedafter 6 min at 160° C. or after 3 min at 180° C. Brittle films wereobtained.

Example 24

Preparation of a film by curing a poly ketone functional compound and aadipic dihydrazide dispersion or a carbohydrazide dispersion.

The products of example 5, 6 and 7 and a mixture 20% of example 7+80% ofexample 5 were mixed with a stoichiomeric amount of the adipicdihydrazide dispersion of example 15 A or with the carbodihydrazidedispersion of example 16. The products were applied onto release paper.The films were cured at 160° C. during 3 min. The film formation wascomplete. The films of the cured product of examples 5 and 6 were verysoft, sticky and flexible. The film of the cured mixture was flexibleand the film of the cured product of example 7 was very hard.

Example 25

Preparation of a film by curing a polyanhydride functional compound anda adipic dihydrazide dispersion. 20 gr of the styrene/anhydridecopolymers, known as SMA 1000, SMA-2000 and SMA 3000 obtainable from ElfAtochem were mixed with 8 g of 1-methoxy-propanol at 80° C. until themixtures were dissolved. The solutions were cooled down and mixed with astoichiometric amount of the adipic dihydrazide dispersion of example 15A or with the carbohydrazide dispersion of example 16 and applied ontoglass or onto release paper. The mixtures were cured at 160° C. for 6min onto glass or for 4 min onto release paper. The coatings obtainedwere extremely hard and brittle.

Example 26

Preparation of a coated textile to be used as synthetic leather.

A coated textile was prepared by direct coating comprising:

-   -   Preparation of an adhesion coat onto textile: 150 μm of a        mixture of 100 g RU-4049, 0.7 g of RM-4456, 5.0 g of XR-S580 and        5 g water (products obtainable from Stahl Holland) was applied        onto textile by knife over roll and the coated textile was dried        for 3 min at 80° C.    -   Preparation of a coat from a solvent free material onto the thus        obtained coated textile: 400μ of a mixture of 100 g of the        product of Example 1 and 21 g of the adipic hydrazide dispersion        of example 15 A was applied onto the coated textile. The coating        was cured in an oven at 1600 for 3 min.    -   The coating was embossed at 190° C.

Example 27

Preparation of a double sided coated textile which may be used assynthetic leather.

A double sided coated textile was prepared by direct coating byrepeating the procedure of example 26 onto the other side of thetextile.

Example 28

Preparation of a coated textile to be used as synthetic leather bytransfer coating.

A coated textile was prepared by transfer coating comprising:

-   -   Preparation of a topcoat onto release paper: 150 μm of a 1:1        mixture of RU-3952 and RU3953 (both are aqueous polyurethane        dispersions obtainable from Stahl Holland) containing 10% of        PP-3215 (a black pigment obtainable from Stahl Holland) was        applied onto release paper by knife over roll and the coated        paper was dried at 80° C. for 3 min.    -   Preparation of an intermediate coat from a solvent free material        onto the coated release paper: 400 μm of a mixture of 100 g of        the product of Example 1 and 21 g of the adipic hydrazide        dispersion of example 15 A was applied onto the topcoat. The        coating on the paper was cured in an oven at 160° C. for 3 min.    -   Preparation of an adhesive coat onto the obtained intermediate        coat: 150 μm of SU-6241 (which is a solvent based polyurethane        obtainable from Stahl Holland) containing 5% of XR-8041 (which        is a crosslinker obtainable from Stahl Holland) was applied onto        the intermediate coat.    -   A piece of textile was laminated into the adhesive and the thus        obtained material was dried at 120° C. for 2 min.    -   The release paper was removed from the thus coated textile.

Example 29

Preparation of a coated materials by transfer coating.

The procedure of example 28 was repeated with the exception that thetextile was replaced by leather, nonwoven or a coagulated polyurethanesubstrate.

Example 30

Preparation of a coated polyvinylchloride to be used as syntheticleather by transfer coating.

-   -   Preparation of a skincoat onto release paper: 150 μm of        EX-51-550 (a solvent based polyurethane dispersions obtainable        from Stahl Holland) was applied onto release paper by knife over        roll and the coated paper was dried at 80° C. for 3 min.    -   Preparation of a coat from a high solids material onto the        coated release paper: 400 μm of a mixture of 100 g of the        product of Example 2 and 17 g of the adipic hydrazide dispersion        of example 15 A was applied onto the topcoat. The coating on the        paper was cured in an oven at 1600 for 3 min.    -   Preparation of a compact polyvinylchloride substrate onto the        high solids coat: 400 μm of a polyvinylchloride paste was        applied onto the high-solids coat.    -   a piece of textile was laminated in the polyvinyl chloride paste        and the polyvinyl chloride was cured by 2 min at 160° C.        followed by 1 min at 220° C.    -   the release paper was removed from the thus coated        polyvinylchloride on textile.

Example 31

Preparation of a moulded material by inmould coating.

A mixture of 100 g of example 2, 20 g ofN,N′,N″-tris(6-isocyanatohexyl)isocyanurate and 37 g of the adipichydrazide dispersion of example 15 A was diluted with 50 g ofbutylacetate and heated to 50° C. while mixing. The mixture was sprayedinto a metalic matrix until a coating of about 400 μm was obtained; thematrix was pretreated with a silicon and was heated at 180° C. duringthe spray process. The matrix was cooled down and the moulded materialwas removed.

1. A process for the preparation of a coating, adhesive, film or sheetwherein a mixture of a polyisocyanate functional, a polyepoxidefunctional, a polyanhydride functional or a polyketone functionalcompound or polymer and a dispersion of a compound containing reactivehydrogen, which compound is a polyhydrazide, a polysemicarbazide, or apolysulphonylhydrazide, in a material which contains no groups which arereactive toward the compound containing reactive hydrogen, in whichmixture the reactivities of the isocyanate, epoxide, anhydride or theketone functions towards the hydrazide, semicarbazide, orsulphonylhydrazide is absent or low at ambient conditions and thereactivities are high at temperatures of 50 to 300° C., is applied ontoa substrate at ambient temperature, followed by reacting the abovecompounds at 50 to 300° C. for 1 to 10 min, or is applied onto asubstrate at ambient temperature, followed by immersing the coatedsubstrate into water of 20 to 100° C. for 1 to 10 min, so that themixture cures completely.
 2. The process according to claim 1, whereinat ambient temperature said compound containing reactive hydrogen is asolid material, a powder, a granule, a flake or grind or a mixturethereof.
 3. The process according to claim 2 wherein size of the grindof said compound containing reactive hydrogen is from 0.5 to 200 μm. 4.The process according to claim 1, wherein said polyhydrazide is selectedfrom the group consisting of oxalic dihydrazide, malonic dinydrazide,succinic dinydrazide, adipic dihydrazide, sebacic dihydrazide,dodecanoic dihydrazide, isophthalic dihydrazide, piperazineN,N′-dihydrazide, m-benzene-dihydrazide, and p-benzene-dihydrazide. 5.The process according to claim 1, wherein said polyhydrazide comprisesadipic dihydrazide.
 6. The process according to claim 1, wherein saidpolysemicarbazide is selected from the group consisting ofethane-disemicarbazide, butane-disemicarbazide, propane-disemicarbazide,hexane-disemicarbazide, para-benzene-disemicarbazide,tuluene-2,4-disemicarbazide, tuluene-2,4-disemicarbazide, bis(4-semicarbazido-phenyl)ether, bis (4,4′-hydrozide)-3,3′-dimethoxybiphenyl, di-N,N′-methylamino urea, 4,4′-methylene-bis (cyclohexenesemicarbazide),3-semicarbazidemethyl-3,5,5-trimethylcyclohexyl-semicarbazide andmixtures thereof.
 7. The process according to claim 1, wherein saidpolysulphonyl hydrazide is selected from the group consisting ofp,p′-oxybis benzene sulphonyl hydrazide, bis(methylhydrazido)sulphate,bis (methylhydrazidosulphonyl)piperazine, and bisp-(hydrazidosulphonylamino)benzene.
 8. The process according to claim 1,wherein the material which contains no groups which are reactive towardsthe compound containing reactive hydrogen, is a polyether, a polyester,a polycarbonate, a polyacrylate, a polyvinylalkylether, a polyurethane,a polyacrylate, a polyvinylalkylether, or a polyurethane.
 9. The processaccording to claim 1, wherein said mixture of the polyisocyanatefunctional, the polyepoxy functional, or the polyketone functionalcompound or polymer and the compound containing reactive hydrogen, issolvent free.
 10. The process according to claim 1, wherein saidpolyisocyanate functional compound or polymer and said compoundcontaining reactive hydrogen are mixed together in an equivalent ratioof 0.5 to 1.5, applied onto a substrate and the so obtained covered orimpregnated substrate is heated to a temperature of 50 to 300° C. for 1to 10 min.
 11. The process according to claim 1, wherein saidpolyisocyanate functional compound or polymer and said compoundcontaining reactive hydrogen are mixed together in an equivalent ratioof 0.5 to 1.5, and applied onto a substrate whereafter the covered orimpregnated substrate is immersed into water of 20 to 100° C. for 1 to10 min.
 12. Coatings, coated substrates, adhesives, films, sheets,impregnated substrates, synthetic leathers, in mold coatings, coatedleathers, coated polyvinylchlorides, coated non-wovens, coatedcoagulated polyurethane substrates, and breathable coated substrates,obtained by applying the process of claim
 1. 13. A coating mixture to beapplied in the process of claim 1 wherein the coating mixture comprisesa mixture of a polyisocyanate functional, a polyepoxyde functional, apolyanhydride functional or a polyketone functional compound and adispersion of a compound containing reactive hydrogen, which compound isa polydydrazide, a polysemicarbazide, or a polysulphonylhydrazide, in amaterial which contains no groups which are reactive towards thecompound containing reactive hydrogen, in which mixture the reactivitiesof the isocyanate, epoxide, anhydride or the ketone functions towardsthe hydrazide or semicarbazide sulphonylhydrazide is absent or low atambient conditions and the reactivities are high at temperatures of 50to 300° C. or when the mixture is immersed into water.
 14. A coatingmixture according to claim 1, wherein the mixture of the polyisocyanatefunctional compound, the polyepoxide functional compound, thepolyanhydride functional compound or the polyketone functional compoundor polymers thereof and the compound containing reactive hydrogen isstable at ambient temperature for at least one day.
 15. A coatingmixture according to claim 13, wherein the mixture of the polyepoxidefunctional compound, the polyanhydride functional compound or thepolyketone functional compound or polymers thereof and the compoundcontaining reactive hydrogen is stable at ambient temperature as a onepot system.
 16. A coating mixture according to claim 13, wherein thecompound containing reactive hydrogen is present as grind which isdispersed in a material which is non-reactive towards the materialcontaining reactive hydrogen.
 17. A coating mixture according to claim13, wherein at ambient temperature the compound containing reactivehydrogen is a solid, which is a powder, a granule, a flake or a grind ora mixture thereof.
 18. A coating mixture according to claim 17, whereinparticle size of the grind or of the dispersion of the compoundcontaining reactive hydrogen is from 0.5 to 200 μm.